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Four types of bismuth oxides, Na3Bi3O8, NaBiO3, α-Bi2O3, and ε-Bi2O3, had been obtained by hydrothermal reactions using NaBiO3·nH2O in NaOH solution. The crystal construction of a unique phase (Na3 Bi3+)Bi25+O8 ((Na0.75Bi0.25)2BiO4) was dependant on making use of single crystal X-ray diffraction data, and also this ingredient had been found to exhibit a Na2MnCl4-related construction with a monoclinic system (space team, Pm) utilizing the following lattice parameters